1-(alpha-hydroxy-beta-trichloroethyl)-dicyclo-pentadiene and di- and tetrahalo derivatives thereof



United States Patent Office 3,410,912 Patented Nov. 12, 1968 3,410,912l-(a-HYDROXY ,8 TRICHLOROETHYL)-DICYCLO- PENTADIENE AND DI- ANDTETRAHALO DE- RIVATIVES THEREOF Herman A.=Bruson, Woodbridge, and HowardL. Plant, Milford, Conn., assignors to Olin Mathieson ChemicalCorporation, a corporation of Virginia No Drawing. Filed Oct. 4, 1965,Ser. No. 492,882 5 Claims. (Cl. 260-617) ABSTRACT OF THE DISCLOSURE Thisinvention relates to new derivatives of dicyclopentadiene having theformula:

wherein A and A are each a divalent radical selected from the groupconsisting of:

which complete the dicyclopentadiene ring system.

According to this invention, the above new compounds are obtained byreacting dicyclopentadiene with chloral in the presence of aFriedel-Crafts catalyst under anhydrous conditions; preferably in thepresence of an inert diluent to moderate the exothermic reaction; andoptionally thereafter adding halogen (chlorine or bromine) to the1-(a-hydroxy 8-trichlor0ethyl)-dicyclopentadiene thus formed. AsFriedel-Crafts catalysts, anhydrous aluminum trichloride, aluminumtribromide, titanium tetrachloride or ferric chloride can 'be used.Typical inert solvents for the reaction are petroleum ether, hexane orethylene dichloride.

It is already known that chloral can be condensed with olefins to yieldmixtures of trichloromethyl carbinol derivatives in which the C1 CCHOHgroup is predominantly on an unsaturated carbon atom (J. Colonge and A.Perrot, Bull. Soc. Chim. France, 1957, 204-08). In the case of cyclicolefins, chloral reacts for example, on the unsaturated carbon atom ofcyclohexene to give cyclohexenyl trichloromethyl carbinol as shown below(E. D. Bergman and A. Becker, J. Org. Chem. 23, 1554 (1958)).

In contrast to this, according to the present invention, chloral reactswith dicyclopentadiene exclusively on the allylic carbon atom adjacentto the double bond as shown below to yield 1-( a-hydroxy [3trichloroethyl)-dicyc1opentadiene.

This structure for the product has been confirmed by nuclear magneticresonance and infrared spectra analysis.

The I (a-hydroxy-fl-trichloroethyl)1-dicyclopentadiene, thus obtained,readily adds chlorine or bromine to one or both of its double bonds.These dior tetrahalogen addition products, for example:

(I It; i

CHOH CHOH I I 0 C1 0 C13 are resin-like materials possessing usefulproperties as fire retardants in plastics. Because of their freehydroxyl group they combine with isocyanates to give urethanes, and canthus find application in the manufacture of polyurethane plastics andfoams which are non-combustible. They also possess pesticidal andherbicidal properties.

The following examples which illustrate the invention are to beconsidered not limitative.

EXAMPLE I Three grams of aluminum chloride was added slowly and in smallportions to a stirred, cooled solution of g. of (0.75 mole)dicyclopentadiene (freshly vacuumdistilled) and 73 g. chloral (0.5 mole)in 100 ml. of n-hexane. The temperature was maintained at 5-10 C. duringthe addition period (20 minutes) by means of a bath of Dry Ice-acetonemixture, and at 0-2" C. for an additional two hours in an ice bath. Thereaction mixture was then poured into 350 ml. of cold water, shakenvigorously, the organic layer washed thoroughly several times with waterand then dried over sodium sulfate. Distillation in vacuum of the driedsolution yielded 31 g. of recovered impure dicyclopentadiene and 76 g.of crude product coming over at -167 C./0.2 mm. Refractionation of thiscut in vacuum yielded 59.6 g. of 1- (u-hydroxy-B-trichloroethyl-dicyclopentadiene boiling at 129131 C./0.1 mm.; 11 1.5495, as acolorless viscous liquid which turned pale yellow on standing in air.

Analysis.Calcd for C H CI O: C, 51.50%; H, 4.69%; Cl, 38.09%. Found: C,51.32%; H, 4.63%; CI, 38.20.

It was confirmed by nuclear magnetic resonance and infrared spectrumanalysis that the structure of the prod- Wasz (ll? CHOH CHOHCC13 EXAMPLEII A solution of 219 g. (1.5 moles) chloral and 100 g. (1.5 moles)dicyclopentadiene in 100 ml. of n-hexane was added slowly with stirringand cooling to a slurry of 6 g. anhydrous aluminum chloride in 100 ml.of n-hexane during the course of one hour. The exothermic reaction wasmaintained at 5 to +5 C. by means of intermittent cooling with a dry icebath. The reaction mixture was stirred for an additional two hours at2-3 C. and then shaken vigorously with 350 ml. of cold water. Theseparated organic layer was washed with three 150 ml. portions of water,dried over sodium sulfate and distilled in vacuum. The fraction boilingat 125-175 C./0.l mm. (166 g.) was fractionally redistilled in vacuum toyield 134 g. of 1-(a-hydroxy-fl-trichloroethyl)-dicyclopentadieneboiling at 129-131" C./0.1 mm.

EXAMPLE III (a) Chlorine was bubbled into a cold (O-l0C.) solu' tion of84 g. (0.3 mole) of l-(a-hydroxy-fi-trichloroethyl)-dicyclopentadiene in200 ml. of carbon tetrachloride in the absence of light, until the gainin weight was 42.6 g. (0.6 mole chlorine). Evaporation of the solventand low boilers in vacuum at 6075 C./ 1420 mm. gave a quantitative yieldof the tetrachloro derivative having the formula:

Cl i C1 CH: 01 o1 CJHOI-I CC]:

Br Br CH2 Br Br CHOH-CGla was obtained as an amber-colored, rosin-likematerial.

(c) One (1) mole equivalent of chlorine as a 10 percent solution ofchlorine in carbon tetrachloride was added at -5C. to a stirred 20 percent solution of one (1) mole equivalent of1-(u-hydroxy-fl-trichloroethyl)- dicyclopentadiene in carbontetrachloride kept in the dark. After evaporation of volatile materialsas in (a) above, the dichloro-adduct of1-(a-hydroxy-fi-trichloroethyl)-dicyclopentadiene was obtained as athick oil.

((1) The dichloro-aduct obtained in (c) above was reacted with one (1)mole equivalent of bromine in carbon tetrachloride solution to give aresinous product which was a mixture of the dichloroand dibromo adductsof 1-(ahydroxy-fi-trichloroethyl)-dicyclopentadine.

Reaction of chloral with dicyclopentadiene The temperature of thisreaction can be varied from about -30 to about 50C. depending upon thepar ticular solvent employed and upon the other reaction conditionsselected. However, the preferred reaction range is from about to about+20C. The molar proportions of chloral reacted with dicyclopentadienecan be varied over a wide range and generally will be from about 0.5 toabout moles of chloral per mole of dicyclopentadiene utilized.

The quantity of the Friedel-Crafts catalyst employed can likewise bevaried widely from about 0.01 to about 1 mole of the catalyst per moleof dicyclopentadiene utilized. The preferred range of catalystconcentration, however, is from about 0.01 to about 0.1 mole of thecatalyst per mole of dicyclopentadiene.

Reaction of 1-(a-hydroxy-B-trichloroethyl)-dicyclopentadiene with ahalogen The halogenation reaction is preferably carried out in thepresence of an inert organic solvent. Useful inert organic solventsinclude, for example, chlorinated hydrocarbons such as carbontetrachloride, ethylene dichloride; lower dialkyl ethers such as diethylether; saturated aliphatic hydrocarbons such as low boiling petroleumether, ligroin, or hexane.

In the preferred embodiment of the halogenation reaction, a solution ofthe l-(a-hydroxy 3 trichloroethyl)- dicyclopentadiene is contacted withgaseous chlorine or bromine or with a solution of the halogen in asuitable solvent. The halogenation reaction can also be conductedemploying liquid chlorine or bromine. Generally, the temperature of thisreaction will be from about 10 to about +50C. and preferably will befrom about 5 to about +20C.

What is claimed is:

1. A compound having the formula:

OH CH CHOH wherein A and A' are each a divalent radical selected fromthe group consisting of:

with the proviso that one of A and A is selected from the groupconsisting of:

and

2. The compound having the formula:

I CH3 GHOH 3. The compound having the formula:

CH2 Cl 01 (HIGH o 01 5 4. The compound having the formula:

Br Br 01-h Br Br CHOH 013 5. A method for the preparation of thecompound:

which comprises reacting under anhydrous conditions at a temperature ofabout -30C. to about 50C. dicyclopentadiene with chloral in the presenceof a Friedel- Crafts catalyst, there being from about 0.5 to about 1.5

moles of chloral reacted per mole of dicyclopentadiene.

References Cited UNITED STATES PATENTS 5 2,814,639 11/1957 Bartlett etal. 260-617 3,118,913 1/1964 Carlson 260617 3,238,251 3/1966 Williams260-617 3,268,597 8/1966 Clemons et al. 260-632 10 FOREIGN PATENTS1,350,242 12/1963 France.

OTHER REFERENCES 15 Broquet: Ann. Chim. (Paris), vol. 3, pp. 204l2Vilkas et al.: Bull. Chim. Soc. Fr., 1955, pp. 799- 805.

LEON ZITVER, Primary Examiner. T. G. DILLAHUNTY, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,410,912 November 12 1968 Herman A. Bruson et al.

hat error appears in the above identified It is certified t patent andthat said Letters Patent are hereby corrected as shown below:

Column 2, lines 3 to 10 and column 4, lines 58 to 65 the right-handportion of the formula, each occurrence should appear as shown below:

CHOH

Column 3, line 18, "1420" should read 14-20 Signed and sealed this 24thday of March 1970.

EDWARD M.FLETCHER,JR.

Commissioner of- Patents Attesting Officer

